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On the formation and metal exchangeability of the rare earth element enriched birnessite from the Ytterby mine, Sweden
Stockholm University, Faculty of Science, Department of Geological Sciences.
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

A porous black substance exuding from fractures in an underground tunnel leading to the shaft of the Ytterby mine, Sweden, was observed in 2012 and characterized as a secondary manganese (Mn) oxide in 2015. The oxide was identified in 2017 as a birnessite variety, Mx[Mn(III,IV)]2O4∙(H2O)n  where M usually is Ca, Na and x is around 0.5, but the Ytterby birnessite appears to be unique with M being Ca, Mg but also yttrium and rare earth elements (YREE), constituting up to 2% of the metal content. The biogenic origin of the Ytterby birnessite was established in 2018. Studies of the formation of this unique birnessite phase has progressed during 2018-19 with detailed studies of the hydrochemistry of the fracture water as well of the exchangeability of the metals M in the structure: Na, Ca, Fe and La representing the YREE. Exposure to solutions of  Na, Ca, Fe, and La, respectively (1 M) led to exchanges and altered distribution of the metals constituting M, with a preference of YREE (trivalent) over Ca (divalent) over Na (monovalent), all of similar ionic radii, as well as higher affinity for YREE over Fe(III), being smaller. Fe(III) did not replace Mn(III) in the structure, despite the fact that their radii are almost identical. No discrete new Fe phase was indicated, and the structure of the birnessite phase was almost identical after exchanges of M, as indicated from XRD. The formation of birnessite in the fracture opening on the tunnel wall appears to be a fast and dynamic process, as indicated by a significant depletion of Mn as well as of YREE in the fracture water during the passage over the precipitation zone, from top to bottom.

National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
URN: urn:nbn:se:su:diva-174774OAI: oai:DiVA.org:su-174774DiVA, id: diva2:1365105
Available from: 2019-10-23 Created: 2019-10-23 Last updated: 2019-10-23Bibliographically approved
In thesis
1. Microbially mediated manganese oxides enriched in yttrium and rare earth elements in the Ytterby mine, Sweden
Open this publication in new window or tab >>Microbially mediated manganese oxides enriched in yttrium and rare earth elements in the Ytterby mine, Sweden
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Microorganisms are able to manipulate redox reactions and thus exert extensive control on chemical speciation and element partitioning in nature, affecting the formation and dissolution of certain minerals. One of these redox active elements is manganese (Mn), which in its oxidized states (III/IV), commonly forms Mn oxide-hydroxide minerals. A microbially mediated birnessite-type Mn oxide enriched in yttrium (Y) and rare earth elements (REE) has been studied in our research. The YREE-enriched birnessite was found in a tunnel to the main shaft of the former Ytterby mine in Sweden, well known as the place of discovery of scandium, yttrium, tantalum and five of the REEs. The thesis aims to define preconditions and processes leading to the formation of this Ytterby birnessite, with particular focus on microbial involvement and the potentially promoting role of biofilms. Dynamics and mineral products of the natural system are studied in combination with analyses of Mn phases produced in vitro by microbes isolated from this system. In addition, the nature of the YREE association with the birnessite-type Mn oxides is investigated.

Natural birnessite has the composition Mx(Mn3+, Mn4+)2O4•(H2O)n  with M ususally being (Na,Ca) and x=0.5. An empirical formula based on element analyses for the Ytterby birnessite has been assessed as M = (Ca0,37-0,41YREE0.02Mg0.04Other metals0.02-0.03), with [Mn3+]/[Mn4+] = 0.86-1.00 to achieve charge balance. We find that there is a preference for the trivalent YREEs over divalent and monovalent metals. There is also a preferential uptake of light rare earth elements (LREE) relative to heavy rare earth elements (HREE), likely due to mineralogical preferences for charge and ionic radius. The YREEs are strongly bound to the mineral structure and not merely adsorbed on the surface. The Mn deposit subsystems (fracture water, Mn oxide precipitating biofilm and bubble biofilm) are phylogenetically significantly different and the microbial community composition of the feeding water has little impact on the derived biofilms. The signature microbial groups of the Mn oxide producing biofilm Rhizobiales (e.g., Pedomicrobium), PLTA13 Gammaproteobacteria, Pirellulaceae, Blastocatellia and Nitrospira are adapted to the specific characteristics of the biofilm: an emerging extreme environment (low temperature, no light, high metal concentration) which is in part generated by the biofilm components themselves. Known Mn oxidizers are identified among these niched microbial groups and four of the isolated bacterial species (Hydrogenophaga sp., Pedobacter sp., Rhizobium sp. and Nevskia sp.) as well as one fungal species (Cladosporium sp.) are involved in Mn oxide production. Hydrogenophaga sp. and Pedobacter sp. produce Mn oxides independently while results imply a synergistic relationship between Rhizobium sp. and selected species. Members of the Pedobacter and Nevskia genera are previously not known to oxidize Mn. Microstructural characterizaton show that the growth pattern of the birnessite-type Mn oxides is either dendritic/shrublike or spherulitic/botryoidal. Nucleation takes place in close association to the biofilm and initial Mn precipitates are observed at different locations depending on the mediating species. Encrustations of cells and other organic structures by Mn precipitates serve as stable nuclei for further growth. The close relationship appears to decrease in importance as the aggregates of poorly crystalline precipitates grow. In the more developed crystals, a repetitive pattern, Liesegang-type of rings, suggests that abiotic factors take over.

Place, publisher, year, edition, pages
Stockholm: Department of Geological Sciences, Stockholm University, 2019. p. 63
Series
Meddelanden från Stockholms universitets institution för geologiska vetenskaper ; 378
Keywords
manganese oxidizers, birnessite, yttrium and rare earth elements (YREE), biofilms, shallow subsurface, Ytterby mine, geomicrobiology, microbial geochemistry, manganoxiderare, birnessit, yttrium och sällsynta jordartsmetaller (YREE), underjordisk, Ytterby mine, geomikrobiologi, mikrobiell kemi
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
urn:nbn:se:su:diva-175390 (URN)978-91-7797-841-1 (ISBN)978-91-7797-842-8 (ISBN)
Public defence
2019-12-11, Nordenskiöldsalen, Geovetenskapens hus, Svante Arrhenius väg 12, 10:00 (English)
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Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Available from: 2019-11-18 Created: 2019-10-23 Last updated: 2019-11-07Bibliographically approved

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